Abstract

Switchable catalysis promises exceptional efficiency in synthesizing polymers with ever-increasing structural complexity. However, current achievements in such attempts are limited to constructing linear block copolymers. Here we report a visible light regulated switchable catalytic system capable of synthesizing hyperbranched polymers in a one-pot/two-stage procedure with commercial glycidyl acrylate (GA) as a heterofunctional monomer. Using (salen)CoIIICl (1) as the catalyst, the ring-opening reaction under a carbon monoxide atmosphere occurs with high regioselectivity (>99% at the methylene position), providing an alkoxycarbonyl cobalt acrylate intermediate (2a) during the first stage. Upon exposure to light, the reaction enters the second stage, wherein 2a serves as a polymerizable initiator for organometallic-mediated radical self-condensing vinyl polymerization (OMR-SCVP). Given the organocobalt chain-end functionality of the resulting hyperbranched poly(glycidyl acrylate) (hb-PGA), a further chain extension process gives access to a core-shell copolymer with brush-on-hyperbranched arm architecture. Notably, the post-modification with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) affords a metal-free hb-PGA that simultaneously improves the toughness and glass transition temperature of epoxy thermosets, while maintaining their storage modulus.

Switchable catalysis promises exceptional efficiency in synthesizing polymers with increasing structural complexity but current achievements in such attempts are limited to constructing linear block copolymers. Here the authors report a visible light regulated switchable catalytic system capable of synthesizing hyperbranched polymers in a one-pot/two-stage procedure with commercial glycidyl acrylate as a heterofunctional monomer.

Details

Title
One-pot synthesis of hyperbranched polymers via visible light regulated switchable catalysis
Author
Zhu, Shuaishuai 1 ; Zhao, Maoji 1 ; Zhou, Hongru 1 ; Wen, Yingfeng 1 ; Wang, Yong 1   VIAFID ORCID Logo  ; Liao, Yonggui 1 ; Zhou, Xingping 1 ; Xie, Xiaolin 1 

 Huazhong University of Science and Technology, School of Chemistry and Chemical Engineering, Wuhan, China (GRID:grid.33199.31) (ISNI:0000 0004 0368 7223) 
Pages
1622
Publication year
2023
Publication date
2023
Publisher
Nature Publishing Group
e-ISSN
20411723
Source type
Scholarly Journal
Language of publication
English
ProQuest document ID
2789891340
Copyright
© The Author(s) 2023. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.